IR multiple photon dissociation spectroscopy of MO2+ (M = V, Nb, Ta)

Wensink, Frank J.; Münst, Maximilian G.; Heller, Jakob; Ončák, Milan; Bakker, Joost M.; Linde, Christian van der

doi:10.1063/5.0024675

Cited by 10 publications

(16 citation statements)

References 45 publications

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“…The experiments were carried out in an FTICR-MS instrument coupled to a FELICE beamline , with a laser vaporization source described earlier. , Pt + ions were produced by irradiating a rotating Pt disk by a frequency-doubled Nd:YAG laser operating at 30 Hz and producing ∼3 mJ pulses. To cool the ions formed and to entrain them in a supersonic expansion when exiting the source region, a pulse of He carrier gas was injected through a piezoelectric valve prior to ablation.…”

Section: Methodsmentioning

confidence: 99%

“…In our experiment, the reaction conditions are a closer match to the single-collision conditions of the experiments by Irikura and Beauchamp . After a fixed reaction time in our RF ion trap, all ions were transferred to the Fourier-transform ion cyclotron resonance mass spectrometer (FTICR-MS) coupled to the Free Electron Laser for IntraCavity experiments (FELICE). − Here, the high photon flux provided by FELICE can be employed to fragment the [Pt,2C,4H] + and [Pt,4C,8H] + ions formed, something Wheeler et al could not achieve with the conventional FELIX beam line . Finally, use of the FTICR-MS instrument allows products of interest to be mass-isolated, foregoing the need to rely on messenger tagging and enhancing the experimental sensitivity.…”

Section: Introductionmentioning

confidence: 98%

“…The FELICE Rayleigh length of 82 mm leads to an IR fluence in cell 4 that is 14 times lower than in cell 1. 27,29 Computational Section. To interpret the experimental IR spectra and to rationalize product formation pathways, density functional theory (DFT) calculations were carried out.…”

Section: ■ Introductionmentioning

confidence: 99%

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C–H Bond Activation and C–C Coupling of Methane on a Single Cationic Platinum Center: A Spectroscopic and Theoretical Study

et al. 2022

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We spectroscopically investigated the activation products resulting from reacting one and multiple methane molecules with Pt + ions. Pt + ions were formed by laser ablation of a metal target and were cooled to the electronic ground state in a supersonic expansion. The ions were then transferred to a room temperature ion trap, where they were reacted with methane at various partial pressures in an argon buffer gas. Product masses observed were [Pt,C,2H] + , [Pt,2C,4H] + , [Pt,4C,8H] + , and [Pt,2C,O,6H] + , which were mass-isolated and characterized using infrared multiple-photon dissociation (IRMPD) spectroscopy employing the free electron laser for intra-cavity experiments (FELICE). The spectra for [Pt,2C,4H] + and [Pt,4C,8H] + have several well-defined bands and, when compared to density functional theory-calculated spectra for several possible product structures, lead to unambiguous assignments to species with ethene ligands, proving Pt + -mediated C–C coupling involving up to four methane molecules. These findings contrast with earlier experiments where Pt + ions were reacted in a flow-tube type reaction channel at significantly higher pressures of helium buffer gas, resulting in the formation of a Pt(CH 3 ) 2 + product. Our DFT calculations show a reaction barrier of +0.16 eV relative to the PtCH 2 + + CH 4 reactants that are required for C–C coupling. The different outcomes in the two experiments suggest that the higher pressure in the earlier work could kinetically trap the dimethyl product, whereas the lower pressure and longer residence times in the ion trap permit the reaction to proceed, resulting in ethene formation and dihydrogen elimination.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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C–H Bond Activation and C–C Coupling of Methane on a Single Cationic Platinum Center: A Spectroscopic and Theoretical Study

et al. 2022

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“…We use the FT-ICR mass spectrometer in the optical cavity of the IR Free Electron Laser for Intra-Cavity Experiments (FELICE), 43 demonstrating that the higher fluences available there are able to efficiently excite IRMPD-resistant species (ESI †). [44][45][46] The observed fragmentation products are interpreted by investigating several isomerization and fragmentation pathways using DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

Wiersma

Candian

Bakker

et al. 2021

Phys. Chem. Chem. Phys.

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“…The IRMPD spectra were recorded using the Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometer beam line of the Free Electron Laser for Intra-Cavity Experiments (FELICE), at the FELIX Laboratory in Nĳmegen. The FELICE FT-ICR apparatus, schematically shown in Figure 2a, has been described in detail before (Petrignani et al 2016;Wensink et al 2020). Here, additional experimental details are presented on features of the FELICE FT-ICR that were used for the first time in this work.…”

Section: Methodsmentioning

confidence: 99%

Gas-phase spectroscopy of photostable PAH ions from the mid- to far-infrared

Wiersma,

Candian,

Bakker

et al. 2021

Preprint

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We present gas-phase InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy of cationic phenanthrene, pyrene, and perylene over the 100-1700 cm −1 (6-95 µm) spectral range. This range covers both local vibrational modes involving C-C and C-H bonds in the mid-IR, and large-amplitude skeletal modes in the far-IR. The experiments were done using the 7T Fourier-Transform Ion Cyclotron Resonance (FTICR) mass spectrometer integrated in the Free-Electron Laser for Intra-Cavity Experiments (FELICE), and findings were complemented with Density Functional Theory (DFT) calculated harmonic and anharmonic spectra, matching the experimental spectra well. The experimental configuration that enables this sensitive spectroscopy of the strongly-bound, photo-resistant Polycyclic Aromatic Hydrocarbons (PAHs) over a wide range can provide such high photon densities that even combination modes with calculated intensities as low as 0.01 km•mol −1 near 400 cm −1 (25 µm) can be detected. Experimental frequencies from this work and all currently available IRMPD spectra for PAH cations were compared to theoretical frequencies from the NASA Ames PAH IR Spectroscopic Database to verify predicted trends for far-IR vibrational modes depending on PAH shape and size, and only a relatively small redshift (6-11 cm −1 ) was found between experiment and theory. The absence of spectral congestion and the drastic reduction in bandwidth with respect to the mid-IR make the far-IR fingerprints viable candidates for theoretical benchmarking, which can aid in the search for individual large PAHs in the interstellar medium.

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IR multiple photon dissociation spectroscopy of MO2+ (M = V, Nb, Ta)

Abstract: The following full text is a publisher's version.For additional information about this publication click this link. https://hdl.handle.net/2066/227109Please be advised that this information was generated on 2022-07-11 and may be subject to change.

Cited by 10 publications

References 45 publications

C–H Bond Activation and C–C Coupling of Methane on a Single Cationic Platinum Center: A Spectroscopic and Theoretical Study

C–H Bond Activation and C–C Coupling of Methane on a Single Cationic Platinum Center: A Spectroscopic and Theoretical Study

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

Gas-phase spectroscopy of photostable PAH ions from the mid- to far-infrared

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